CN108918746A - A kind of synchronous instrument and method for detecting water sample molecular weight distribution and organic nitrogen - Google Patents
A kind of synchronous instrument and method for detecting water sample molecular weight distribution and organic nitrogen Download PDFInfo
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- CN108918746A CN108918746A CN201810480696.0A CN201810480696A CN108918746A CN 108918746 A CN108918746 A CN 108918746A CN 201810480696 A CN201810480696 A CN 201810480696A CN 108918746 A CN108918746 A CN 108918746A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000001360 synchronised effect Effects 0.000 title claims abstract description 26
- 238000009826 distribution Methods 0.000 title claims abstract description 20
- 125000001477 organic nitrogen group Chemical group 0.000 title claims abstract description 16
- 238000002347 injection Methods 0.000 claims abstract description 93
- 239000007924 injection Substances 0.000 claims abstract description 93
- 238000001514 detection method Methods 0.000 claims abstract description 59
- 239000001301 oxygen Substances 0.000 claims abstract description 59
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 59
- 239000002253 acid Substances 0.000 claims abstract description 58
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000000926 separation method Methods 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000007853 buffer solution Substances 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 230000029087 digestion Effects 0.000 claims abstract description 26
- 238000006213 oxygenation reaction Methods 0.000 claims abstract description 18
- 238000012545 processing Methods 0.000 claims abstract description 17
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 12
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 40
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 29
- 239000012498 ultrapure water Substances 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- 238000005070 sampling Methods 0.000 claims description 15
- 238000001802 infusion Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 8
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 claims description 8
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229920002530 polyetherether ketone Polymers 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000004587 chromatography analysis Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 238000000520 microinjection Methods 0.000 claims description 4
- 230000003139 buffering effect Effects 0.000 claims description 2
- 239000008055 phosphate buffer solution Substances 0.000 claims description 2
- 238000012512 characterization method Methods 0.000 claims 1
- 230000001934 delay Effects 0.000 claims 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 7
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004457 water analysis Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 35
- 230000000694 effects Effects 0.000 description 12
- 239000002699 waste material Substances 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000007812 deficiency Effects 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 6
- 229940124530 sulfonamide Drugs 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
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- 231100000719 pollutant Toxicity 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
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- 238000001542 size-exclusion chromatography Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
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- -1 polydimethylsiloxanes Polymers 0.000 description 2
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- 241000208340 Araliaceae Species 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 206010019133 Hangover Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GQENKOUTFPKGLE-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3].[OH4+2] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3].[OH4+2] GQENKOUTFPKGLE-UHFFFAOYSA-N 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000003149 assay kit Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000010291 electrical method Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/182—Specific anions in water
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/067—Preparation by reaction, e.g. derivatising the sample
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N2030/645—Electrical detectors electrical conductivity detectors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1826—Organic contamination in water
- G01N33/1846—Total carbon analysis
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Abstract
The present invention relates to a kind of synchronous detection water sample molecular weight distribution and the instrument and method of organic nitrogen, which includes the end injection valve being linked in sequence by pipeline, chromatographic column, pressure reducing valve, acid adding injection valve, oxygenation injection valve, sour oxygen reaction helix tube, CO2Remover, UV digestion device, the second gas-water separation film, buffer solution injection valve, buffer solution reaction helix tube, cadmium column, color developing agent injection valve, color developing agent react helix tube, UV detector, the end injection valve connects CO for receiving mobile phase and sample, the second gas-water separation film2Electric conductivity detector, the UV detector, CO2Electric conductivity detector is connect with the computer for data processing.The present invention realizes sample to be tested in the synchronous detection of the TOC concentration, DON concentration of different molecular weight distributed area, provides reliable convenient and fast detection means for field of water quality detection such as water factory's Inlet and outlet water water analysis, nitrogenous disinfection byproducts Detection & Controling.
Description
Technical field
The present invention relates to technical field of environmental detection, more particularly, to a kind of synchronous detection water sample molecular weight distribution and organic
The instrument and method of nitrogen.
Background technique
China is vast due to national territorial area at present, and freshwater resources total amount is higher, occupies the 4th, the world, accounts for global water money
The 6% of source total amount.But due to populous, freshwater resources occupancy volume per person only ranks 121 in the world, sees in this way, in
State is still the serious country of water shortage.Although freshwater resources occupancy volume per person's wretched insufficiency, various water environment pollution situations exist
It is in all parts of the country still repeatedly to occur, such as the abuse of organic agricultural chemicals, personal-care supplies, Powdered Detergent Containing Phosphate etc., industrial wastewater without
Disorderly row leaves about for processing, and agricultural, animal husbandry sewage are discharged into the behaviors such as water body.These behaviors just further polluting we are only,
Rare water resource." prevention "+" improvement " is needed to advance side by side the improvement of water environment pollution：It first has to pick up from source, shut out
Exhausted polluter is directly discharged to the generation of this kind of contaminant water environmental phenomenons in water body without processing after up to standard.Secondly, subtracting
While of low pollution object is discharged into water body, we also need to carry out the water body polluted comprehensive effective improvement.
How to realize that " suiting the remedy to the case " is always to be engaged in water pollution control scholar research when administering water environment pollution
Hot spot.There has been proposed be similar to advanced oxidation processes, the administering methods such as membrane separation process.Although these methods can be effectively by pollution
Degradation of pollutant in water body all inevitably occurs that dosage is big, " cannot suit the remedy to the case " to reduced levels
Problem.There have been the secondary pollution due to caused by medicament excess, the problems such as treatment process is uneconomical easily occur when administering for this.
The key solved these problems is that more comprehensively more accurately water quality data is grasped before improvement, has only thoroughly understood and has got dirty
The most comprehensive accurately water quality data for contaminating water body, could provide foundation to the promotion of water treatment technology, so that proposition is more accurate
Resolution.
The acquisition of polluted water body water quality data relies on better water quality inspection technique, and traditional water quality detection is
Water sample is obtained from polluted water body, is then transported into laboratory, using a series of analytical instrument of water quality, to polluted-water
Water quality characterized, to obtain water quality data.But such water quality detection has following deficiency：
1, in detection process, the acquisition of different types of water quality data be all it is separated, thus the specific aim of water quality data
It reduces.For example illustrate：Contained by analysis water-like when TOC concentration, it can not accomplish to analyze DON content simultaneously, then this moment
The TOC concentration and DON concentration of such water sample be it is independent, more targetedly water quality cannot be characterized.Such as Shimadzu
Though TOC analyzer be able to achieve the detection of TOC concentration, even if after increasing total nitrogen (TN) module, the inspection of two parameters
It surveys distance and is still independently operated, and cannot still accomplish the synchronous detection of DON concentration.The more ginsengs of the series of HACH company of the U.S.
Number Water Test Kits, though can be realized the detection to parameters such as TN, ammonia nitrogen concentrations, which is exactly by several measurement modules
It is grouped together, the operation of actually modules is still independent, can not in addition as Shimadzu TOC analyzer
It realizes and the synchronous of DON concentration is detected.Unlike above-mentioned detecting instrument, the present invention utilizes once oxidation, can
Realize and TOC concentration, the synchronous of DON concentration detected, to further improve the specific aim of water quality data, realize to water quality into
Row full width multi-dimensions test.
2, DON concentration is difficult to accomplish accurately to detect at present, but it is most important to drinking water water supply security.For example, in water
The research field of novel nitrogen-containing disinfection by-products in factory, in order to guarantee that disinfection by-products is especially novel at present in water factory's water outlet
The amount of nitrogenous disinfection byproducts needs the amount of the different strict control disinfectants according to influent quality, because of nitrogenous disinfection by-product
One of source of object is exactly the DON in raw water, has understood the size of water inlet DON concentration, is discharged nitrogenous disinfection for control
The amount of by-product is most important.The Master's thesis of Harbin Institute of Technology Zhang Jing《Organic nitrogen concentration based on dialysis power-up principle
Detect preprocess method research》The domestic and international deficiency in relation to DON concentration detection method at present is discussed, and proposes dialysis and adds
The method of electrical method detection DON concentration.This method truly has raising for the accuracy of DON Concentration Testing, but the detection time expended
Long, detection efficiency is low, complicated for operation in detection process, these deficiencies are also the common fault of most of detection DON concentration method.It is real
Testing the room detection common differential technique of DON has that total nitrogen subtracts inorganic nitrogen and total Kjeldahl nitrogen subtracts two kinds of ammonia nitrogen, and both methods needs
Repeated detection, the systematic error accumulated in this way is larger, and the influence to result is also larger.Most instrument can only currently on the market
TN, ammonia nitrogen concentration are detected, differential technique is also all based on to the detection of DON concentration, such as：The TN analyzer of the WTW of Germany, in fact
It is exactly the combination of three modules, the detection for DON concentration, the instrument is carried out also with above-mentioned differential technique.With mention above
Unlike the detecting instrument arrived, the detection to DON concentration is can be thus achieved using the separation of chromatographic column in the present invention, convenient and efficient
Accurately.It compensates at present for the deficiency of DON concentration detection method.
The deficiency of above-mentioned water quality detection brings difficulty to the acquisition of current polluted-water water quality data, also cannot
More accurate control measures are provided.The improvement of current water environment pollution needs one kind and can synchronize to detect different pollutants
TOC concentration and DON concentration in different molecular weight section.The patent disclosure of Patent No. 2015101472555 one kind
The instrument and method of detection TOC, TN and TP concentration can be synchronized, although which can be realized the synchronous inspection of three kinds of indexs
It surveys, but for the detection of TN concentration using direct ultraviolet spectrophotometry, i.e. DON generates nitrate nitrogen after being oxidized,
Then the ultraviolet light irradiation of 220nm is directly used, nitrate nitrogen is detected by the size of absorbance, so that conversion obtains DON's
Concentration, but the detection of this method limit it is higher, and UV signal receive remaining impurity ions interference it is larger, experimental result
Accuracy cannot be guaranteed.In addition, above-mentioned patent still can not achieve the synchronous detection to DON concentration.Another application No. is
The patent of 201610712720X proposes that a kind of online ultraviolet digestion total nitrogen total phosphorus total organic carbon synchronizes the instrument of detection, the patent
TN concentration be also ultraviolet lamp irradiation to be located using 220nm, and cannot achieve the synchronous of DON concentration and detect.
Detect different pollutants in different molecular weight section in short, can synchronize there are no any one both at home and abroad at present
The instrument of interior TOC concentration and DON concentration or conveniently, accurate detection method.
Summary of the invention
The present invention specifically addresses the deficiency of the polluted-water water quality detection being widely present at present mentioned above, Jin Erti
For a kind of synchronous detection water sample molecular weight distribution and the instrument and method of organic nitrogen.The present invention can synchronize detection water sample to be measured not
With total organic carbon (TOC) concentration of component, soluble organic nitrogen (DON) concentration in molecular weight distribution section.According to existing point
Son amount distribution map, realizes the qualitative and quantitative detection to the different molecular weight component separated.Measurement data can be
It is shown and is stored in the form of chromatogram on computer, and the enterprising traveling of chromatogram can be aggregated by correlation plot software
The analysis of one step.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of synchronous instrument for detecting water sample molecular weight distribution and organic nitrogen, including the end note being linked in sequence by pipeline
Enter valve, chromatographic column, pressure reducing valve, acid adding injection valve, oxygenation injection valve, sour oxygen reaction helix tube, CO2Remover, UV digestion device,
Two gas-water separation films, buffer solution injection valve, buffer solution reaction helix tube, cadmium column, color developing agent injection valve, color developing agent react spiral shell
Coil, UV detector, the end injection valve connect CO for receiving mobile phase and sample, the second gas-water separation film2Electricity
Lead detector, the UV detector, CO2Electric conductivity detector is connect with the computer for data processing.
The end injection valve is connect with sampling pump and sample bottle, the end injection valve also with mobile phase infusion pump and stream
Dynamic phase reagent bottle connection；
The acid adding injection valve is connect with acid solution syringe pump and acid solution bottle；
The oxygenation injection valve is connect with oxygen liquid syringe pump and oxygen liquid bottle；
The buffer solution injection valve is connect with buffer solution syringe pump and buffer solution reagent bottle；
The color developing agent injection valve is connect with color developing agent syringe pump and color-developer reagent bottle.
The CO2Remover includes the first gas-water separation film, collection gas coil pipe, stripping pump and diaphragm, first air water point
It is connected from film, collection gas coil pipe and diaphragm sequence, and the first gas-water separation film reacts helix tube with sour oxygen by pipeline and connect,
The diaphragm is connect by outlet snorkel and pipeline with suprasil helix tube, and the stripping pump is connect with collection gas coil pipe, institute
The effect for stating the first gas-water separation film is the CO for generating IC acidification2It is separated with liquid component, and then enters in collection gas coil pipe and receive
Collection gets up, and the first gas-water separation film is preferably PDMS membrane, belongs to oxygen permeable membrane, to CO2Have well
Separating effect, and stable structure.The effect of the diaphragm is by the CO in air2It is isolated in outside, prevents from entering component to be measured
In.The effect of the stripping pump is to provide stripping power, will collect the CO collected in gas coil pipe2Stripping is gone out, and the stripping pump is excellent
Choosing is minitype pneumatic diaphragm pump, and compact can effectively provide stripping power, cheap.
The UV digestion device includes heater strip, suprasil helix tube and UV lamp, and the suprasil helix tube passes through pipe
Road is connected between the diaphragm and the second gas-water separation film, and the UV lamp is located at the top of suprasil helix tube, described to add
Heated filament is located at the lower section of suprasil helix tube.
The second gas-water separation film is connected between UV digestion device and buffer solution injection valve, second gas-water separation
Film connects CO2Electric conductivity detector, the CO for will be generated in UV digestion device2It separates to CO2In electric conductivity detector, remaining sample into
Enter buffer solution injection valve, and then enter back into UV detector, the second gas-water separation film is preferably polydimethylsiloxanes
Alkane film, belongs to oxygen permeable membrane, to CO2There are good separating effect, and stable structure.
The CO2Electric conductivity detector includes ultrapure water tank, ultrapure water pump and the conductance cell being linked in sequence, the oxidation of UV digestion device
Sample afterwards passes through gas-liquid separation membrane, by the CO of generation2It separates and is dissolved in by the drive of ultrapure water pump, it is net by ion
Change inside the ultrapure water that resin purification is crossed, then pass in conductance cell, is examined by detecting the variation of conductance cell liquid electric conductivity
Survey CO2Amount, and pass through certain conversion relation and characterize TOC concentration.
Preferably, ultrapure water selects the production of Milli-Q ultrapure water instrument, resistivity is 18.2M Ω, and ultrapure water pump is selected micro-
Type infusion pump, it is 0.01 μ s/cm -300 μ s/cm that conductance cell, which selects measurement range, and resolution ratio is the conductivity electrode of 0.01 μ s/cm
Flow cell.
The chromatographic column is located in chromatographic column column oven.
The UV detector is connect with waste liquid barrel.
The UV detector is connect by UV detector data line with the computer for data processing, the CO2Conductance
Detector passes through CO2Electric conductivity detector data line is connect with the computer for data processing.
Using the synchronous detection water sample molecular weight distribution of above-mentioned instrument and the method for organic nitrogen, include the following steps：
Sample collects in pipeline by sampling pump, is mixed by end injection valve with the flowing conveyed by infusion pump,
Then pass through the liquid chromatogram post separation in chromatographic column incubator, the component in sample is successively flowed out according to the difference of molecular weight, so
It is depressurized afterwards by pressure reducing valve, by pressure reduction to about 1 atmospheric pressure, the sample different molecular weight component isolated passes through pipeline
Successively pass through acid adding injection valve and oxygenation injection valve, the acid solution syringe pump of acid solution pipeline can be infused according to the amount of setting to acid adding at this time
Enter valve injection acid solution, the oxygenation syringe pump of oxygen liquid pipeline can inject oxygen liquid to oxygenation injection valve according to the amount of setting at this time, then
Component, mobile phase, acid solution and oxygen liquid to be measured sufficiently react in sour oxygen reaction helix tube；Inorganic carbon (IC) can quilt in component to be measured
Acid solution acidification generates CO2, by subsequent CO2Remover stripping is into air.The component to be measured of inorganic carbon has been removed by pipeline
Further in UV digestion device, the TOC in component can be oxidized to CO under ultraviolet light irradiation and heating condition2, DON oxygen
Nitrate nitrogen is turned to, the sample after oxidation passes through gas-liquid separation membrane, by the CO of generation2It separates and enters CO2Electric conductivity detector
In, CO2Electric conductivity detector detects CO2Amount, and TOC concentration is characterized by certain conversion relation, it is hereafter remaining without TOC
Buffer solution is added into component by buffer solution injection valve for component, then passes through Cadmium column reduction, nitrate nitrogen is reduced to
Then color developing agent is added by color developing agent injection valve in nitrite nitrogen, then mix in color developing agent reaction helix tube anti-
It answers, finally enters in UV detector, the amount of nitrite nitrogen is detected at 540nm, and DON is characterized by certain conversion relation
Concentration, after detection, UV detector exports waste liquid and CO2Electric conductivity detector waste liquid is discharged to waste liquid barrel by sewer pipe.
The chromatographic column uses liquid phase size exclusion chromatography post, and the valid interval that molecular weight is distinguished can be according to the need of user
Self-setting is wanted, generally can choose as 500~800000Da.
The mobile phase should be selected according to the requirement of chromatographic column, be typically chosen in phosphate buffer solution, and ion is strong
Degree is 0.1~0.4M, and pH is 6.8 ± 0.2.
The mobile phase infusion pump flow rate pump should ensure that each chromatographic peak appearance is sharply easily distinguished, and it is existing that hangover does not occur
As, and it is general to can choose as 0.4~1.0mL/min in the flow rates that chromatographic column allows.The mobile phase is defeated
Liquid pump pressure will generally may be selected to be 1.8 ± 0.2MPa in the pressure limit that chromatographic column allows.
The chromatographic column column oven band heater strip, column oven column temperature should be adjusted according to the appearance situation of sample, and one
Aspect will guarantee that each chromatographic peak peak width is relatively narrow, on the other hand will also be within the temperature range of chromatographic column allows, general color
The peak width of spectral peak substantially 4~10min, temperature are traditionally arranged to be 30~60 DEG C.
The sampling pump collects sample in pipeline, mixes by end injection valve and flowing.
The sampling pump selects micro-injection pump, and pump work pressure should be higher than that 1500psi, full accuracy should be less than 0.1%,
The conveying of no pulse formula, conveying uniform can be distributed accurately from very small to very big injection volume.Sampling volume should be ensured that color
Spectral peak appearance is sharp and easily distinguishes, and can be selected according to the effect of chromatography post separation, general to be arranged in 50~500uL.
For filling acid solution, acid solution should select the acid solution bottle according to the difference of sample, but will guarantee IC all acid
Turn to CO2, it is general can be selected as 15%~30% phosphoric acid.
The oxygen liquid bottle should be selected for filling oxygen liquid, the oxygen liquid according to the difference of sample, and the oxygen liquid will guarantee TOC
All it is oxidized to CO2, it is general can be selected as 10%~20% ammonium persulfate solution.
The acid solution syringe pump and oxygen liquid syringe pump should be able to be injected into acid solution and oxygen into primary flow path according to certain flow velocity
Liquid, and will not flow velocity to primary flow path and pressure have an impact.Preferably：Micro-injection pump, pump work pressure should be higher than that
1500psi, less than 0.1%, the conveying of no pulse formula can be distributed accurately from very small to very big injection volume full accuracy,
Acid adding oxygenation pipeline is connected with sample pipe using injection valve.Sour oxygen injection flow rate pump should ensure that sour oxygen solution is excessive, can basis
The concentration selection of sample and sour oxygen solution, it is general to can choose as 1.0~4.0 μ L/min.
The end injection valve, acid adding injection valve, oxygenation injection valve, buffer solution injection valve, color developing agent injection valve are all
Meeting can be stable slow by a kind of liquid, and stable being added in another liquid mixes, and will not generate suck-back.It is preferred that
Be：Injection valve with cut-off plate and cushion, cut-off plate prevent liquid reflux suck-back, and caching pad helps to delay liquid stabilising
Slowly it is injected into another liquid.
The acid oxygen reaction helix tube is arranged between UV digestion device and oxygenation injection valve, is to guarantee that IC is sufficiently acidified
CO2, preferably：It is formed using stainless steel PEEK pipe spiral.One side cost reduces；Another aspect stainless steel PEEK pipe can have
Effect prevents medicament from corroding and guaranteeing that the component to be measured separated will not mix again wherein.
The buffer solution reagent bottle uses ammonium chloride buffer solution, passes through for filling buffer solution, the buffer solution
85.0g ammonium chloride and bis- ethylenediamine hydrate tetraacethyl disodium of 1.0g are dissolved in 800mL water, and constant volume to 1000mL mixes.It is molten
The pH value of liquid is preferably 8.5.
The color developing agent preparation is as follows, is dissolved in 600mL water using 100mL phosphoric acid, the salt of 40g sulfanilamide (SN) and 1g is then added
Sour naphthodiamide, is diluted with water to 1000mL mixing, and the phosphoric acid Analysis about Selection is pure.
The purpose of the cadmium column is that the nitrate nitrogen after oxidation is reduced to nitrite nitrogen, and the reduction efficiency of cadmium column should
Higher than 98%, the filling of cadmium column will facilitate, and be hardly damaged.
The buffer solution reaction helix tube and color developing agent reaction helix tube are preferably：Using stainless steel PEEK pipe spiral shell
It revolves.One side cost reduces；Another aspect stainless steel PEEK pipe can effectively prevent medicament from corroding and guaranteeing to isolate
The component to be measured come will not mix again wherein.
The amount of the buffer solution will be determined according to actual water sample.The flow velocity of the color developing agent syringe pump will guarantee to be added
Color developing agent it is excessive, it is general to can choose as 1.0~4.0 μ L/min.
The UV digestion device includes suprasil reaction helix tube, UV lamp and heater strip.Suprasil reacts helix tube
The space of enough reactions is provided, under UV lamp irradiation and heating condition, the active oxide material over cure acid group of oxidant generation
Free radical can be fully oxidized by component to be measured.Preferably, UV lamp wavelength is 190nm, heating temperature is set as (95 ± 2 DEG C).
The UV detector meets the variation of on-line checking absorbance, equipped with flow through sample pond, and by result store with
And it is output to computer and is further analyzed.As preferably, the UV detector band PEEK pipe fitting can be examined online
It surveys, draws the Ultraviolet Detector of chromatogram automatically using software.
The instrument internal sample inlet material is in order to avoid sample etches, preferably stainless steel PEEK pipe.Primary flow path
Flow velocity be mobile phase infusion pump flow rate pump, may be selected to be 0.4~1.0mL/min.Be 1.8 before pressure liquid chromatography column ±
0.2MPa, it is 1bar that liquid-phase chromatographic column passes through pressure reducing valve pressure later, and fluidised form is to flow freely.
The present invention can synchronize the TOC concentration for detecting component of the water sample to be measured in different molecular weight distributed area, and DON is dense
Degree.Specifically testing principle is：
Sample is passed through into size exclusion chromatography post, sample component is according to point in the range of selection chromatography post separation in water outlet
Son amount size arrangement, then the most common two water quality parameter TOC concentration in detection different molecular weight distributed area and DON are dense
Degree.The invention utilizes the different molecular weight component in the water sample by size exclusion chromatography separation successively to flow according to molecular size range
Out, in conjunction with the detection to TOC concentration in the present invention, can accurately recognize different molecular weight distribution situation and
TOC concentration in different molecular weight distributed area.It is tested, is obtained true at some repeatedly according to a large amount of nitrogenous standard samples
In the fixed residence time, that flow out chromatographic column is DON, detection of the cooperation present invention to DON, thus convenient and efficient efficiently and accurately
The DON concentration determined in water sample to be measured.
That is, the present invention can provide component of the synchronous detection water sample to be measured in different molecular weight distributed area
TOC concentration, DON concentration.Analysis time greatly shortens, and is more importantly, the present invention can realize contaminant water in complete meaning
The synchronous acquisition of body water quality data.
Technology path of the invention is：
Firstly, the sample in sample bottle passes through the transmission of sampling pump, reach in pipeline, and be injected by end injection valve
In mobile phase pipeline.Mobile phase in Mobile-phase reagent bottle is transferred in primary flow path under the action of mobile phase infusion pump, is reached
It is mixed after the injection valve of end with sample.Mobile phase carries sample by the chromatography post separation in chromatographic column column oven.By color
After composing post separation, sample to be tested is successively flowed out according to its component molecular amount size, and passes through pressure reducing valve, and pressure reduction is one big
Air pressure, fluidised form are free discharge.Subsequent component to be measured reaches acid adding injection valve and oxygenation injection valve in primary flow path, and through peracid
Liquid syringe pump and the acid solution of oxygen liquid syringe pump transmission, the mixing of oxygen liquid, further in sour oxygen reaction helix tube.Mobile phase, to
It surveys component, acid solution and oxygen liquid and is sufficiently mixed reaction in sour oxygen reaction spiral.
In sour oxygen reaction spiral, IC is CO by thorough acidification2(reaction 1)
Inorganic carbon (IC) in component to be measured is acidified by acid solution, the CO of generation2It is blended in pipeline, into CO2Remover,
By the CO of generation2It separates, and is discharged into air from liquid phase.CO2The structure of remover is as described above：Wherein, generation
CO2It is separated from liquid phase by the first gas-water separation film immediately, enters in collection gas coil pipe, pump and transmit by stripping, by CO2Through
It gets into the air after crossing diaphragm stripping, and the CO in air2By septum barrier, will not enter in liquid phase.
The remaining component and mobile phase to be measured for eliminating IC moves on, into UV digestion device.The structure of UV digestion device
As described above：Suprasil reacts helix tube and provides reaction compartment, and component to be measured, mobile phase, oxygen liquid and acid solution are filled wherein
Divide mixing auger to advance, under the conditions of the irradiation of UV lamp and electric-heating-wire-heating, TOC is oxidized to CO2, DON is oxidized to nitre
Acid ion (reaction 2,3).
The CO that TOC oxidation at this time generates2It into the second gas-water separation film, is opened with liquid phase separation, into CO2Conductivity detection
In device.CO2Electric conductivity detector structure is as described above, wherein the CO separated2CO is entered by another flow path2Electric conductivity detector
In, it is dissolved in ultrapure water lines.Ultrapure water is driven by ultrapure water pump, is drawn from ultrapure water tank, and CO is being dissolved2Afterwards
Into in conductance cell, CO is detected by the variation of conductance2Content so that represent TOC concentration.
The component for eliminating TOC later reaches buffer solution injection valve, the buffering conveyed at this time with buffer solution syringe pump
Solution mixing reaches after buffer solution reaction helix tube further mixes and enters in cadmium column, the nitrate nitrogen that oxidation is generated
It is reduced to nitrite nitrogen, is mixed at color developing agent injection valve with the color developing agent of color developing agent syringe pump conveying later, and developing the color
Further is reacted in agent reaction helix tube, using under acid medium, nitrite nitrogen and sulfanilamide (SN) carry out diazo-reaction, then with
Hydrochloride naphthodiamide coupling generates purplish red color substance.
It finally enters in UV detector, generates absorption under nm ultraviolet light using nitrite nitrogen, and uptake meets ratio
That law, obtaining signal by photoelectric sensor, passing through processing obtains the amount of nitrite nitrogen later, is closed according to certain conversion
System, and then further characterize out DON concentration.
Conductance cell outlet waste water and UV detector outlet waste water are collected in waste liquid barrel after converging.The data of sum have number respectively
According to transmission line and it is sent to computer end, is further stored and is handled.
Outlet waste water is collected in waste liquid barrel after converging.UV detector is by UV detector data line and is used for data processing
Computer connection, CO2Electric conductivity detector passes through CO2Electric conductivity detector data line is connect with the computer for data processing, is counted
Calculation machine is further stored and is handled.
Compared with prior art, technical characterstic of the invention and advantage are as follows：
1, synchronism.One instrument can synchronize qualitative detection and go out polluted-water sample in different molecular weight distribution areas
TOC the and DON concentration of component in interior constituent species, and the different molecular weight distribution sections of synchronous quantitative detection out.
2, comprehensive.Instrument data obtained broken in the past can only one data point of a sample detection pattern,
Realize breakthrough of the sample data from point to face.
3, specific aim.Instrument of the present invention it is initiative by sample to be tested by detecting different molecular after chromatography post separation
TOC the and DON concentration of the contaminant component in distributed area is measured, water quality data more has specific aim, to later nitrogenous
The research of disinfection by-products has important support meaning.
4, accuracy.The initiative method for proposing liquid chromatography separation and surveying DON concentration of instrument of the present invention, the method phase
Compared with traditional differential technique, accuracy is greatly improved.
5, simplicity.The initiative method for proposing liquid chromatography separation and surveying DON concentration of instrument of the present invention, compared to state
Inside and outside common dialyser, ion exchange column, pre-concentration and catalytic reduction method, it is easy to operate, it is automatic to carry out, it substantially increases
The efficiency of water quality detection.
Detailed description of the invention
Fig. 1 is the apparatus structure schematic diagram of the synchronous detection water sample molecular weight distribution of the present invention and organic nitrogen；
Fig. 2 is CO2Remover structural schematic diagram；
Fig. 3 is UV digestion device structural schematic diagram.
Figure label：1- Mobile-phase reagent bottle；2- mobile phase infusion pump；The end 3- injection valve；4- sampling pump；5- sample
Bottle；6- chromatographic column；7- chromatographic column column oven；8- pressure reducing valve；9- acid adding injection valve；10- acid solution syringe pump；11- acid solution bottle；12-
Oxygenation injection valve；13- oxygen liquid syringe pump；14- oxygen liquid bottle；15- acid oxygen reacts helix tube；16-UV digestion device；17- buffer solution
Syringe pump；18- buffer solution reagent bottle；19- buffer solution injection valve；20- buffer solution reacts helix tube；21- cadmium column；22-
Color developing agent injection valve；23- color developing agent syringe pump；24- color-developer reagent bottle；25- color developing agent reacts helix tube；26-UV detector；
27- waste liquid barrel；28- computer；29- heater strip；30- suprasil helix tube；31-UV lamp；32-CO2Remover；33- second
Gas-water separation film；34-CO2Electric conductivity detector；The ultrapure water tank of 35-；The ultrapure water pump of 36-；37- conductance cell；The first gas-water separation of 38-
Film；39- collection gas coil pipe；40- stripping pump；41- diaphragm；42- exports snorkel；43-UV detector data line；44-CO2Conductance inspection
Survey device data line.
Specific embodiment
With reference to Fig. 1, a kind of synchronous instrument for detecting water sample molecular weight distribution and organic nitrogen, including pass through pipeline and be linked in sequence
End injection valve 3, chromatographic column 6, pressure reducing valve 8, acid adding injection valve 9, oxygenation injection valve 12, sour oxygen react helix tube 15, CO2It goes
Except device 32, UV digestion device 16, the second gas-water separation film 33, buffer solution injection valve 19, buffer solution react helix tube 20, cadmium column
21, color developing agent injection valve 22, color developing agent react helix tube 25, UV detector 26, and the end injection valve 3 is for receiving mobile phase
With sample, the second gas-water separation film 33 connects CO2Electric conductivity detector 34, the UV detector 26, CO2Electric conductivity detector 34
It is connect with the computer 28 for data processing.
Wherein, the end injection valve 3 is connect with sampling pump 4 and sample bottle 5, and the end injection valve 3 is gone back and mobile phase
Infusion pump 2 and Mobile-phase reagent bottle 1 connect；The acid adding injection valve 9 is connect with acid solution syringe pump 10 and acid solution bottle 11；It is described to add
Oxygen injection valve 12 is connect with oxygen liquid syringe pump 13 and oxygen liquid bottle 14；The buffer solution injection valve 19 and buffer solution syringe pump 17
And buffer solution reagent bottle 18 connects；The color developing agent injection valve 22 connects with color developing agent syringe pump 23 and color-developer reagent bottle 24
It connects.The chromatographic column 6 is located in chromatographic column column oven 7.The UV detector 26 is connect with waste liquid barrel 27.The UV detector 26
It is connect by UV detector data line 43 with the computer 28 for data processing, the CO2Electric conductivity detector 34 passes through CO2Electricity
Detector data line 44 is led to connect with the computer 28 for data processing.
With reference to Fig. 2, the CO2Remover 32 includes the first gas-water separation film 38, collection gas coil pipe 39, stripping pump 40 and diaphragm
41, the first gas-water separation film 38, collection gas coil pipe 39 and diaphragm 41 are sequentially connected, and the first gas-water separation film 38 passes through
Pipeline is connect with sour oxygen reaction helix tube 15, and the diaphragm 41 passes through outlet snorkel 42 and pipeline and suprasil helix tube 30
Connection, the stripping pump 40 are connect with collection gas coil pipe 39, and the effect of the first gas-water separation film 38 is to be acidified IC to generate
CO2It is separated with liquid component, and then enters in collection gas coil pipe and collect, the first gas-water separation film 38 is preferably poly- two
Methylsiloxane film, belongs to oxygen permeable membrane, to CO2There are good separating effect, and stable structure.The effect of the diaphragm 41
By the CO in air2It is isolated in outside, prevents from entering in component to be measured.The effect of the stripping pump 40 is to provide stripping power,
The CO collected in gas coil pipe 39 will be collected2Stripping is gone out, the stripping pump 40 preferably minitype pneumatic diaphragm pump, compact,
Stripping power can be effectively provided, it is cheap.
With reference to Fig. 3, the UV digestion device 16 includes heater strip 29, suprasil helix tube 30 and UV lamp 31, described transparent
Quartzy helix tube 30 passes through piping connection between the diaphragm 41 and the second gas-water separation film 33, the UV lamp 31 is located at saturating
The top of alum English helix tube 30, the heater strip 29 are located at the lower section of suprasil helix tube 30.
The second gas-water separation film 33 is connected between UV digestion device 16 and buffer solution injection valve 19, second gas
Water seperation film 33 connects CO2Electric conductivity detector 34, the CO for will be generated in UV digestion device 162It separates to CO2Electric conductivity detector 34
In, remaining sample enters buffer solution injection valve 19, and then enters back into UV detector, and the second gas-water separation film 33 is preferably
Be PDMS membrane, belong to oxygen permeable membrane, to CO2There are good separating effect, and stable structure.
The CO2Electric conductivity detector 34 includes ultrapure water tank 35, ultrapure water pump 36 and the conductance cell 37 being linked in sequence, and UV disappears
It solves the sample after device 16 aoxidizes and passes through gas-liquid separation membrane 19, by the CO of generation2It separates and is dissolved in by ultrapure 36 band of water pump
Dynamic, it inside the ultrapure water crossed by ion cleaning resin purification, then passes in conductance cell, by detecting conductance cell liquid electric
The variation of conductance detects CO2Amount, and pass through certain conversion relation and characterize TOC concentration.
Preferably, ultrapure water selects the production of Milli-Q ultrapure water instrument, resistivity is 18.2M Ω, and ultrapure water pump is selected micro-
Type infusion pump, it is 0.01 μ s/cm -300 μ s/cm that conductance cell, which selects measurement range, and resolution ratio is the conductivity electrode of 0.01 μ s/cm
Flow cell.
Technology path of the invention is as shown in Figure 1：
Firstly, the sample in sample bottle 5 passes through the transmission of sampling pump 4, reach in pipeline, and by 3 note of end injection valve
Enter into mobile phase pipeline.Mobile phase in Mobile-phase reagent bottle 1 is transferred to primary flow path under the action of mobile phase infusion pump 2
In, it is mixed after reaching end injection valve 3 with sample.Mobile phase carries sample and divides by the chromatographic column 6 in chromatographic column column oven 7
From.After the separation of chromatographic column 6, sample to be tested is successively flowed out according to its component molecular amount size, and passes through pressure reducing valve 8, pressure
It is reduced to an atmospheric pressure, fluidised form is free discharge.Subsequent component to be measured reaches acid adding injection valve 9 and oxygenation note in primary flow path
Enter valve 12, mixes with by acid solution syringe pump 10 and the acid solution of the transmission of oxygen liquid syringe pump 13, oxygen liquid, reacted further to sour oxygen
In helix tube 15.Mobile phase, component to be measured, acid solution and oxygen liquid are sufficiently mixed reaction in sour oxygen reaction spiral 15.
In sour oxygen reaction spiral 15, IC is CO by thorough acidification2(reaction 1)
Inorganic carbon (IC) in component to be measured is acidified by acid solution, the CO of generation2It is blended in pipeline, into CO2Remover
16, by the CO of generation2It separates, and is discharged into air from liquid phase.CO2The structure of remover 16 is as shown in Figure 2：Wherein,
The CO of generation2It is separated, is entered in collection gas coil pipe 39 from liquid phase by the first gas-water separation film 38 immediately, by stripping pump 40
Transmission, by CO2It gets into the air after 41 stripping of diaphragm, and the CO in air2It is blocked, will not be entered in liquid phase by diaphragm 41.
The remaining component and mobile phase to be measured for eliminating IC moves on, into UV digestion device.The knot of UV digestion device 16
Structure is as shown in Figure 3：Suprasil reacts helix tube and provides reaction compartment, and component to be measured, mobile phase, oxygen liquid and acid solution are wherein
It is sufficiently mixed and is threadingly advanced, under 29 heating condition of irradiation and heating wire of UV lamp 31, TOC is oxidized to CO2, by DON oxygen
Turn to nitrate ion (reaction 2,3).
The CO that TOC oxidation at this time generates2It into the second gas-water separation film 33, is opened with liquid phase separation, into CO2Conductance inspection
It surveys in device 34.CO234 structure of electric conductivity detector is as shown in figure 1 shown in dotted line frame：Wherein, the CO separated2Entered by another flow path
CO2In electric conductivity detector, it is dissolved in ultrapure water lines.Ultrapure water is driven by ultrapure water pump, is drawn from ultrapure water tank,
Dissolving CO2Enter in conductance cell afterwards, CO is detected by the variation of conductance2Content so that represent TOC concentration.
The component for eliminating TOC later reaches buffer solution injection valve 19, conveys at this time with buffer solution syringe pump 17
Buffer solution mixing reaches after buffer solution reaction helix tube 20 further mixes and enters in cadmium column 21, oxidation is generated
Nitrate nitrogen is reduced to nitrite nitrogen, mixes at color developing agent injection valve 22 with the color developing agent of the conveying of color developing agent syringe pump 23 later
It closes, and is further reacted in color developing agent reaction helix tube 25, using under acid medium, nitrite nitrogen and sulfanilamide (SN) carry out diazonium
Change reaction, then generates purplish red color substance with hydrochloride naphthodiamide coupling.
It finally enters in UV detector 26, generates absorption under 540nm ultraviolet light using nitrite nitrogen, and uptake accords with
Beer law is closed, obtaining signal by photoelectric sensor, passing through processing obtains the amount of nitrite nitrogen later, changes according to certain
Calculation relationship, and then further characterize out DON concentration.
Conductance cell 37 exports waste water and UV detector 26 is exported after waste water converges and collected in waste liquid barrel 27.23 and 33 number
According to there is data transmission link 35 and 34 to be sent to computer end 36 respectively, is further stored and handled.
Outlet waste water is collected in waste liquid barrel 27 after converging.UV detector 26 passes through UV detector data line 43 and is used to count
It is connected according to the computer 28 of processing, CO2Electric conductivity detector 34 passes through CO2Electric conductivity detector data line 44 with for data processing
Computer 28 connects, and computer 28 is further stored and handled.
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment
Preparation：
Instrument booting, opens computer 28.Mobile phase is carried out to the ultrasonic degassing processing of 20min, to eliminate in mobile phase
Bubble, in order to avoid interference detection results.Sample is crossed into 0.45 μm of film, to remove granule foreign, in order to avoid instrument is caused to block.Setting
The temperature of good chromatographic column column oven.In UV digestion device 16, UV lamp wavelength is set as 190nm, and heating temperature is set as 95 DEG C.It opens
UV detector 26, Detection wavelength is set as 540nm.Ultrapure water pump 36 is opened, allows CO2Ultrapure water starts to flow in detector.Clearly
Empty waste liquid barrel 27.
Operating procedure：
Etc. after preparations, open mobile phase infusion pump 2, set flow velocity and pressure.Equal 28 baseline of computers
After stabilization (general 1~2h), the sampling volume of sampling pump, sour oxygen syringe pump, buffer solution syringe pump, color developing agent injection are set
Sampling pump 4, acid solution syringe pump 10, oxygen liquid syringe pump 13, buffer solution syringe pump 17, color developing agent syringe pump are opened after flow rate pump
23.Sample is injected into mobile phase by end injection valve 3, acid solution and oxygen liquid are injected into mobile phase, wait number later
According to result.
The main chromatographic condition section of the present embodiment is as follows：
The different molecular weight standard specimen residence time obtained according to TOC concentration chromatogram peak is as follows：
It is as a result as follows using bovine serum albumin as DON Concentration Testing sample：
The detection of TOC concentration：Method provided by the invention is 0.03 μ g/L~50mg/L for TOC concentration inspection range；
The detection of DON concentration：When the detection light path of UV detector is 10mm, method provided by the invention is for DON
Concentration mensuration range is 0.12mg/L~10mg/L.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. the instrument of a kind of synchronous detection water sample molecular weight distribution and organic nitrogen, which is characterized in that including being connected by pipeline sequence
End injection valve (3), chromatographic column (6), pressure reducing valve (8), acid adding injection valve (9), oxygenation injection valve (12), the sour oxygen reaction spiral shell connect
Coil (15), CO2Remover (32), the second gas-water separation film (33), buffer solution injection valve (19), delays UV digestion device (16)
Rush solution reaction helix tube (20), cadmium column (21), color developing agent injection valve (22), color developing agent reaction helix tube (25), UV detector
(26), the end injection valve (3) connects CO for receiving mobile phase and sample, the second gas-water separation film (33)2Conductance
Detector (34), the UV detector (26), CO2Electric conductivity detector (34) connects with the computer (28) for data processing
It connects.
2. the instrument of a kind of synchronous detection water sample molecular weight distribution according to claim 1 and organic nitrogen, which is characterized in that
The end injection valve (3) connect with sampling pump (4) and sample bottle (5), and the end injection valve (3) is gone back and mobile phase infusion pump
(2) and Mobile-phase reagent bottle (1) connects；
The acid adding injection valve (9) connect with acid solution syringe pump (10) and acid solution bottle (11)；
The oxygenation injection valve (12) connect with oxygen liquid syringe pump (13) and oxygen liquid bottle (14)；
The buffer solution injection valve (19) connect with buffer solution syringe pump (17) and buffer solution reagent bottle (18)；
The color developing agent injection valve (22) connect with color developing agent syringe pump (23) and color-developer reagent bottle (24).
3. the instrument of a kind of synchronous detection water sample molecular weight distribution according to claim 1 and organic nitrogen, which is characterized in that
The CO2Remover (32) includes the first gas-water separation film (38), collection gas coil pipe (39), stripping pump (40) and diaphragm (41), institute
It states the first gas-water separation film (38), collection gas coil pipe (39) and diaphragm (41) sequence to be connected, and the first gas-water separation film (38)
It is connect by pipeline with sour oxygen reaction helix tube (15), the diaphragm (41) is connect by pipeline with UV digestion device (16), described
Stripping pumps (40) and connect with collection gas coil pipe (39).
4. the instrument of a kind of synchronous detection water sample molecular weight distribution according to claim 3 and organic nitrogen, which is characterized in that
The UV digestion device (16) includes heater strip (29), suprasil helix tube (30) and UV lamp (31), the suprasil spiral
(30) are managed through piping connection between the diaphragm (41) and the second gas-water separation film (33), the UV lamp (31) is located at transparent
The top of quartzy helix tube (30), the heater strip (29) are located at the lower section of suprasil helix tube (30).
5. the instrument of a kind of synchronous detection water sample molecular weight distribution according to claim 1 and organic nitrogen, which is characterized in that
The CO2Electric conductivity detector (34) includes ultrapure water tank (35), ultrapure water pump (36) and the conductance cell (37) being linked in sequence, and UV disappears
Sample after solving device (16) oxidation is after gas-liquid separation membrane (19) by the CO of generation2It is dissolved in and is driven by ultrapure water pump (36)
Ultrapure water in, be passed through in conductance cell, the variation by detecting conductance cell liquid electric conductivity detects CO2Amount.
6. using the synchronous detection water sample molecular weight distribution of instrument described in claim 1 and the method for organic nitrogen, which is characterized in that packet
Include following steps：
Sample collects in pipeline, mixes with flowing, then passes through chromatography post separation, the component in sample is according to molecular weight
It is different successively to flow out, it is then depressurized by pressure reducing valve, the sample different molecular weight component isolated is by pipeline successively by adding
Sour injection valve and oxygenation injection valve, to acid adding injection valve inject acid solution, to oxygenation injection valve inject oxygen liquid, then component to be measured,
Mobile phase, acid solution and oxygen liquid sufficiently react in sour oxygen reaction helix tube；Inorganic carbon (IC) can be acidified by acid solution in component to be measured
Generate CO2, by subsequent CO2Remover stripping is into air.The component to be measured for having removed inorganic carbon is further arrived by pipeline
Up in UV digestion device, the TOC in component can be oxidized to CO2, DON is oxidized to nitrate nitrogen, and the sample after oxidation passes through gas-liquid
Seperation film, by the CO of generation2It separates and enters CO2In electric conductivity detector, CO2Electric conductivity detector detects CO2Amount, and lead to
Certain conversion relation characterization TOC concentration is crossed, hereafter the remaining component without TOC is molten by buffer solution injection valve addition buffering
Then liquid passes through Cadmium column reduction, nitrate nitrogen is reduced to nitrite nitrogen, colour developing then is added by color developing agent injection valve
Then agent carries out hybrid reaction in color developing agent reaction helix tube, finally enters in UV detector, nitrous is detected at 540nm
The amount of hydrochlorate nitrogen, and DON concentration is characterized by conversion relation.
7. according to the method described in claim 6, it is characterized in that, the mobile phase is selected as phosphate buffer solution, ion
Intensity is 0.1~0.4M, and pH is 6.8 ± 0.2, and the mobile phase infusion pump flow rate pump is selected as 0.4~1.0mL/min, described
Mobile phase infusion pump pressure is selected as 1.8 ± 0.2MPa, and it is 30~60 DEG C that the chromatographic column, which maintains temperature, pressure chromatographic column it
Before be 1.8 ± 0.2MPa, passing through pressure reducing valve pressure after chromatographic column is 1bar, and fluidised form is to flow freely, in the UV digestion device,
UV lamp wavelength is 190nm, and heating temperature is set as 95 ± 2 DEG C.
8. according to the method described in claim 6, it is characterized in that, the sampling pump selects micro-injection pump, pump work pressure
Higher than 1500psi, full accuracy is less than 0.1%, and sampling volume is in 50~500uL, the acid solution syringe pump and oxygen liquid syringe pump
Micro-injection pump is selected, pump work pressure is higher than 1500psi, and full accuracy is less than 0.1%, the conveying of no pulse formula, the acid solution
Syringe pump and oxygen liquid injection flow rate pump are selected as 1.0~4.0 μ L/min, and the flow velocity of the color developing agent syringe pump is selected as 1.0~
4.0μL/min。
9. according to the method described in claim 6, it is characterized in that, the end injection valve, acid adding injection valve, oxygenation inject
Valve, buffer solution injection valve, color developing agent injection valve are all to meet：Can be stable slow by a kind of liquid, stable being added to is another
It is mixed in a kind of liquid, and suck-back will not be generated.
10. according to the method described in claim 6, it is characterized in that, the acid oxygen reaction helix tube, buffer solution react spiral
Pipe, color developing agent reaction helix tube are all made of stainless steel PEEK pipe spiral and form, and instrument internal sample inlet selects stainless steel PEEK
Pipe.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810480696.0A CN108918746A (en) | 2018-05-18 | 2018-05-18 | A kind of synchronous instrument and method for detecting water sample molecular weight distribution and organic nitrogen |
| PCT/CN2018/102945 WO2019218530A1 (en) | 2018-05-18 | 2018-08-29 | Instrument and method for simultaneously testing molecular weight distribution and organic nitrogen level of water sample |
| US17/056,425 US11796525B2 (en) | 2018-05-18 | 2018-08-29 | Instrument and method for simultaneously testing molecular weight distribution and organic nitrogen level of water sample |
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| CN201810480696.0A CN108918746A (en) | 2018-05-18 | 2018-05-18 | A kind of synchronous instrument and method for detecting water sample molecular weight distribution and organic nitrogen |
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| US (1) | US11796525B2 (en) |
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| CN109358128A (en) * | 2018-12-03 | 2019-02-19 | 南京大学 | A kind of organic nitrogen-organic carbon tandem online test method and device |
| CN109406705A (en) * | 2018-11-29 | 2019-03-01 | 南京大学 | A kind of liquid chromatogram combination type organic carbon detector and its application method |
| CN110082447A (en) * | 2019-05-09 | 2019-08-02 | 同济大学 | Synchronous characterization water sample Dissolved Organic Matter structure/physics and chemistry/grey density characteristics instrument |
| WO2019218530A1 (en) * | 2018-05-18 | 2019-11-21 | 同济大学 | Instrument and method for simultaneously testing molecular weight distribution and organic nitrogen level of water sample |
| CN111707744A (en) * | 2020-06-11 | 2020-09-25 | 同济大学 | Instrument and method for synchronously representing physicochemical/optical characteristics of organic matter to be detected |
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| CN109709057B (en) * | 2018-12-29 | 2021-12-07 | 四川碧朗科技有限公司 | Water quality index prediction model construction method and water quality index monitoring method |
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Also Published As
| Publication number | Publication date |
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| WO2019218530A1 (en) | 2019-11-21 |
| US20210208116A1 (en) | 2021-07-08 |
| US11796525B2 (en) | 2023-10-24 |
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